Water-and oil-repellent

ABSTRACT

A water- and oil-repellent includes, as an active ingredient, a fluorine-containing copolymer including as a copolymer unit (A) at least one of perfluoroalkylalkyl acrylates and corresponding methacrylates, (B) benzyl acrylate or benzyl methacrylate represented by the general formula: C n F 2n+1 C m H 2m OCOCR═CH 2  (wherein R represents a hydrogen atom or a methyl group; n represents 4, 5, or 6; and m represents 1, 2, 3, or 4), (C) a fluorine-free polymerizable monomer other than benzyl acrylate and benzyl methacrylate, and (D) a cross-linkable group-containing polymerizable monomer.

RELATED APPLICATION

This application is a 35 U.S.C. §371 national phase filing ofInternational Patent Application No. PCT/JP2008/064278, filed Aug. 8,2008, through which and to which priority is claimed under 35 U.S.C.§119 to Japanese Patent Application Nos. 2007-265084, filed Oct. 11,2007 and 2008-130304, filed May 19, 2008.

TECHNICAL FIELD

The present invention relates to a water- and oil-repellent. Morespecifically, the present invention relates to a water- andoil-repellent that allows water- and oil-repellent treatment at lowcuring temperature and imparts good textile feeling to a water- andoil-repellent-treated fabric.

BACKGROUND ART

The expression of water- and oil-repellency results from the low surfaceenergy of fluorine, and, usually, fluorine-containing acrylate polymersare widely used as active ingredients of water- and oil-repellents.Previous various investigations have shown that the presence ofcrystallinity in a fluorine-containing polymer is necessary forexpressing water- and oil-repellency in practical applications. Inparticular, it has been recognized that the hydrophobicity of afluorine-containing polymer depends on the number of carbon atoms of aside-chain fluoroalkyl group and that the expression of crystallinity isobserved when the number of carbon atoms is eight or more.

[Non-Patent Document 1] Secchaku (Adhesion), Vol. 50, No. 5, pp. 16-22(2006)

Therefore, it has been regarded that a fluorine-containing polymerhaving a short fluoroalkyl group, i.e., a side-chain fluoroalkyl grouphaving 7 or less, in particular, 6 or less carbon atoms, is low in ordoes not have crystallinity and thereby cannot provide water-repellentperformance that is sufficient for practical use. In addition, sincewater- and oil-repellents are required to have washing resistance andabrasion resistance, fluorine-containing acrylic polymers having longside chains are used.

However, polymers including a side-chain fluoroalkyl group having 8 ormore carbon atoms are very hard due to their high crystallinity and havea problem that flexibility of textile products is impaired. Furthermore,since the water-repellent process needs high curing temperature, thereare problems such as a change in color of fibers. In addition, since thepolymers including a long side-chain fluoroalkyl group having 8 or morecarbon atoms are excessively hydrophobic, a large amount of anemulsifier is necessary for producing a water- and oil-repellent.

The present applicant has before proposed a water- and oil-repellentcomposed of an aqueous emulsion in which a copolymer of a fluoroalkylgroup-containing polymerizable monomer and vinylidene chloride orbenzyl(meth)acrylate, and a carboxyl group-containing water-solublepolymer are dispersed in water using a nonionic surfactant. Thefluoroalkyl group of a fluoroalkyl group-containing polymerizablemonomer that is copolymerized with vinylidene chloride orbenzyl(meth)acrylate is recognized to be a perfluoroalkyl group having 4to 20 carbon atoms, but the perfluoroalkyl group used in theabove-mentioned polymerization example is recognized to be a mixture ofperfluoroalkyl groups having 6 to 14 carbon atoms, 9.0 on average.

[Patent Document 1] JP-A-11-80710

Accordingly, it is believed that a water- and oil-repellent showingexcellent in flexibility and also excellent in washing resistance can beobtained if water- and oil-repellency can be expressed with afluorine-containing polymer including a short side-chain fluoroalkylgroup having 6 or less carbon atoms.

It has been also proposed a surface-treating agent showing excellentwater repellency, oil repellency, and antifouling property by using apolymer having a short fluoroalkyl group having 1 to 6 carbon atoms asthe side chain, but the fluoroalkyl group-containing monomer usedtherein is a fluorine-containing monomer compound represented by thegeneral formula:Rf—Y—O—CO—CX═CH₂

-   -   X: F, Cl, Br, I, CFX¹X², CN, a fluoroalkyl group having 1 to 20        carbon atoms, benzyl group, or phenyl group,    -   Y: an aliphatic group having 1 to 10 carbon atoms, an aromatic        or alicyclic group having 6 to 10 carbon atoms, a CH₂CH₂NR¹SO₂        group, or a CH₂CH(OY¹)CH₂ group, and    -   Rf: a fluoroalkyl group having 1 to 6 carbon atoms.        Acrylic acid derivatives in which X is H are shown as        comparative manufacturing examples, and methacrylic acid        derivatives in which X is CH₈ are intendedly excluded.

[Patent Document 2] JP-A-2004-352976

Furthermore, it has been proposed a water- and oil-repellent compositionof which essential component is a copolymer containing as apolymerization unit (a) an Rf group-containing monomer of whichhomopolymer does not have a melting point derived from the Rf group inthe microcrystals or has a melting point of 55° C. or less and has aglass transition point of 20° C. or more and (b) an Rf group-freemonomer having a cross-linkable functional group, wherein thecomposition can impart excellent water- and oil-repellency to products,even in low temperature treatment, and also can perform a water- andoil-repellent process with providing soft textile feeling and alsoexcellent durability.

[Patent Document 3] WO 2004/035708

In the above, a perfluoroalkylalkyl(meth)acrylate is used as thecomponent monomer (a), but a specific monomer, such as a 2-butanoneoxime adduct, pyrazole adduct, or ε-caprolactam adduct of a ω-isocyanatealkyl(meth)acrylate, is used as the component monomer (b) in thecopolymerization reaction.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

It is an object of the present invention to provide a water- andoil-repellent of which an active ingredient is a copolymer of aperfluoroalkylalkyl(meth)acrylate being low in bioaccumulationpotential, wherein the copolymer is not that in which a specific monomeris copolymerized; the curing temperature in water- and oil-repellenttreatment using the copolymer as an active ingredient is low; and afabric treated with the water- and oil-repellent is imparted withexcellent textile feeling.

Means for Solving the Problems

Such an object of the present invention is achieved by a water- andoil-repellent (herein after referred to as a first invention) including,as an active ingredient, a fluorine-containing copolymer including as acopolymerization unit,

(A) at least one of perfluoroalkylalkyl acrylates and correspondingmethacrylates represented by the general formula:C_(n)F_(2n+1)C_(m)H_(2m)OCOCR═CH₂(wherein R represents a hydrogen atom or a methyl group; n represents 4,5, or 6; and m represents 1, 2, 3, or 4),

(B) benzyl acrylate or benzyl methacrylate,

(C) a fluorine-free polymerizable monomer other than benzyl acrylate andbenzyl methacrylate, and

(D) a cross-linkable group-containing polymerizable monomer,

or achieved by a water- and oil-repellent (hereinafter referred to as asecond invention) including, as an active ingredient, afluorine-containing copolymer including as a copolymerization unit,

(a) a perfluoroalkylalkyl acrylate represented by the general formula:C_(n)F_(2n+1)C_(m)H_(2m)OCOCH═CH₂(wherein n represents 4, 5, or 6; and m represents 1, 2, 3, or 4),

(b) a perfluoroalkylalkyl methacrylate represented by the generalformula:C_(n)F_(2n+1)C_(m)H_(2m)OCOC(CH₃)═CH₂(wherein n represents 4, 5, or 6; and m represents 1, 2, 3, or 4),

(c) a fluorine-free polymerizable monomer, and

(d) a cross-linkable group-containing polymerizable monomer.

Effect of the Invention

The water- and oil-repellent according to the present invention is awater- and oil-repellent of which an active ingredient is a copolymer ofa perfluoroalkylalkyl(meth)acrylate being low in bioaccumulationpotential, wherein the copolymer is not that in which a specific monomeris copolymerized; the curing temperature in water- and oil-repellenttreatment using the copolymer as an active ingredient is low; andexcellent textile feeling can be imparted to a water- andoil-repellent-treated fabric. In particular, regarding the textilefeeling, it is recognized an advantageous effect that the fabric afterthe water- and oil-repellent treatment is not hardened, but instead issoftened to improve the textile feeling. In addition, the water- andoil-repellent can impart sufficient water- and oil-repellency not onlyto synthetic fibers but also to natural fibers, and is also excellent inwashing resistance.

When both the perfluoroalkylalkyl acrylate and the perfluoroalkylalkylmethacrylate are used, not only good water-repellency but also goodoil-repellency can be obtained.

Furthermore, in curing for cross-linking between a fabric and the water-and oil-repellent, when the cross-linking temperature for the curing islow, target performance cannot be obtained because of an insufficientreaction, a dropout of the polymer constituting the water- andoil-repellent and so on. Therefore, curing is usually performed underconditions such as at 180° C. for 1 minute or 170° C. for 1 or 2 minutesand is sometimes performed under conditions such as 160° C. for 3minutes. In the water- and oil-repellent of the present invention, asshown in the below-described each Example, curing at a further lowertemperature, at 150° C. for 3 minutes, is possible.

BEST EMBODIMENT FOR CARRYING OUT THE INVENTION

First, the copolymer unit of the first invention will be described.

Preferred examples of the component (A),perfluoroalkylalkyl(meth)acrylate, represented by the general formula:C_(n)F_(2n+1)C_(m)H_(2m)OCOCR═CH₂

-   -   R: a hydrogen atom or a methyl group    -   n: 4, 5, or 6    -   m: 1, 2, 3, or 4        include the following compounds:        C₄F₉CH₂CH₂OCOCH═CH₂,        C₄F₉CH₂CH₂OCOC(CH₃)═CH₂,        C₆F₁₃CH₂CH₂OCOCH═CH₂, and        C₆F₁₃CH₂CH₂OCOC(CH₃)═CH₂.

The component (A), perfluoroalkylalkyl(meth)acrylate, is supplied to acopolymerization reaction in such a ratio that its proportion in theresulting copolymer is about 10 to 80% by weight, preferably about 25 to80% by weight, and more preferably about 40 to 80% by weight. By thecopolymerization of such a monomer component (A), an aqueous dispersionshowing excellent in emulsion stability can be formed, and water- andoil-repellency is expressed.

The component (B), benzyl acrylate or benzyl methacrylate, is suppliedto the copolymerization reaction in such a ratio that its proportion inthe resulting copolymer is about 5 to 80% by weight, preferably about 5to 50% by weight, and more preferably about 5 to 35% by weight. By thecopolymerization of the benzyl(meth)acrylate, the copolymer shows a goodfilm-forming property and orientation.

As the component (C), fluorine-free polymerizable monomer, for example,at least one of vinylidene chlorides, alkyl(meth)acrylates includingstraight-chain or branched alkyl groups having 1 to 18 carbon atoms,cycloalkyl(meth)acrylates, alkoxyalkyl(meth)acrylates includingalkoxyalkyl groups having 2 to 6 carbon atoms, monoalkyl esters ordialkyl esters of maleic acid or fumaric acid including an alkyl grouphaving 1 to 8 carbon atoms, and vinyl esters such as vinyl acetate andvinyl caprylate is preferably used from the balance of water- andoil-repellency. In addition, another examples of the fluorine-freepolymerizable monomer include copolymerizable vinyl compounds, such asstyrene, methylstyrene, α-methylstyrene, vinylnaphthalene,(meth)acrylonitrile, acetone acrylamide, vinyl chloride, chloroethylvinyl ether, a hydroxyalkyl vinyl ether including an alkyl group having1 to 4 carbon atoms, polyethylene glycol mono(meth)acrylate, andpolypropylene glycol mono(meth)acrylate. Furthermore, a diene compoundsuch as isoprene, pentadiene, or butadiene can be copolymerized. In thefirst invention, the vinylidene chloride is preferably used.

The fluorine-free polymerizable monomer other than benzyl(meth)acrylatesis supplied to the copolymerization reaction in such a ratio that itsproportion in the resulting copolymer is about 5 to 80% by weight,preferably about 5 to 60% by weight, and more preferably about 5 to 40%by weight.

Examples of the component (D), cross-linkable group-containingpolymerizable monomer, include epoxy group-containing monomers such asallyl glycidyl ether and glycidyl(meth)acrylate; N-methylolgroup-containing monomers such as N-methylol(meth)acrylamide andN-butoxymethylol(meth)acrylamide; hydroxyalkyl group-containing monomerssuch as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl acrylate,4-hydroxybutyl acrylate, and 2-hydroxy-3-chloropropyl(meth)acrylate;amide group-containing monomers such as (meth)acrylamide, N-methylacrylamide, diacetone acrylamide, and compounds represented by theformula:CH₂═C(CH₃)CON⁻—N⁺(CH₃)₂CH₂CH(OH)CH₃, orCH₂═C(CH₃)CON⁻—N⁺(CH₃)₃;aziridinyl group-containing monomers such asaziridinylethyl(meth)acrylate; and polyol poly(meth)acrylates such asethylene glycol di(meth)acrylate, polyoxyethylene di(meth)acrylate, andpolyoxypropylene glycol di(meth)acrylate. Hydrophilic monomers arepreferably used.

Further copolymerization of the cross-linkable group-containingpolymerizable monomer strengthens the adhesion, to base materials suchas fibers, of the fluorine-containing copolymer used as an activecomponent for water- and oil-repellency; also shows an effect ofimproving, for example, the durability, washing resistance, anddry-cleaning resistance of the water- and oil-repellent; and alsousually gives a secondary effect of improving the polymerizationstability during emulsion polymerization. Therefore, the component (D)is used in such a ratio that its proportion in the copolymer is about0.5 to 40% by weight and preferably about 1 to 15% by weight.

Next, the copolymerization units of the second invention will bedescribed.

Preferable examples of the component (a), perfluoroalkylalkyl acrylate,represented by the general formula:C_(n)F_(2n+1)C_(m)H_(2m)OCOCH═CH₂

-   -   n: 4, 5, or 6    -   m: 1, 2, 3, or 4        include the following compounds:        C₄F₉CH₂CH₂OCOCH═CH₂,        C₅F₁₁CH₂CH₂OCOCH═CH₂, and        C₆F₁₃CH₂CH₂OCOCH═CH₂.

The component (a), perfluoroalkylalkyl acrylate, is supplied to acopolymerization reaction in such a ratio that its proportion in theresulting copolymer is about 1 to 80% by weight, preferably about 5 to40% by weight, and more preferably about 8.5 to 20% by weight. By thecopolymerization of such a monomer component (a), an aqueous dispersionshowing excellent in emulsion stability can be formed, and water- andoil-repellency is expressed.

The preferable examples of the component (b), perfluoroalkylalkylmethacrylate, represented by the general formula:C_(n)F_(2n+1)C_(m)H_(2m)OCOC(CH₃)═CH₂

-   -   n: 4, 5, or 6    -   m: 1, 2, 3, or 4        include the following compounds:        C₄F₉CH₂CH₂OCOC(CH₃)═CH₂,        C₅F₁₁CH₂CH₂OCOC(CH₃)═CH₂, and        C₆F₁₃CH₂CH₂OCOC(CH₃)═CH₂.

The component (b), perfluoroalkylalkyl methacrylate, is supplied to thecopolymerization reaction in such a ratio that its proportion in theresulting copolymer is about 10 to 80% by weight, preferably about 25 to80% by weight, and more preferably about 35 to 60% by weight. By thecopolymerization of such a monomer component (b) to the component (a),an aqueous dispersion showing excellent in emulsion stability can beformed, and further excellent water-repellency and oil-repellency areexpressed.

The various types of the fluorine-free polymerizable monomers shown inthe first invention are used as the fluorine-free polymerizable monomerof the component (c), and at least one of vinylidene chlorides, stearylacrylates, stearyl methacrylates, benzyl acrylates, and benzylmethacrylates is preferably used. The component (c), fluorine-freepolymerizable monomer, is supplied to the copolymerization reaction insuch a ratio that its proportion in the copolymer is about 5 to 80% byweight, preferably about 5 to 60% by weight, and more preferably about 5to 40% by weight.

Furthermore, examples of the component (d), cross-linkablegroup-containing polymerizable monomer, include the same cross-linkablegroup-containing polymerizable monomers shown in the first invention,and hydrophilic monomers are preferably used.

Further copolymerization of the cross-linkable group-containingpolymerizable monomer strengthens the adhesion, to base materials suchas fibers, of the fluorine-containing copolymer used as an activecomponent for water- and oil-repellency; also shows an effect ofimproving, for example, the durability, washing resistance, anddry-cleaning resistance of the water- and oil-repellent; and alsousually gives a secondary effect of improving the polymerizationstability during emulsion polymerization. Therefore, the component (d)is used in such a ratio that its proportion in the copolymer is about0.5 to 40% by weight and preferably about 1 to 15% by weight.

Furthermore, since the copolymerization reaction is performed at apolymerization ratio of 90% or more, the weight ratios of copolymerizedmonomers in the copolymer approximately agree with the weight ratios ofmonomers charged for the copolymerization.

In both the first invention and the second invention, thecopolymerization reaction using these polymerizable monomers isperformed by emulsion polymerization in the presence of a surface-activeemulsifier composed of a polyethylene oxide adduct type nonionicsurfactant or of both said nonionic surfactant and a polyethylene oxideadduct type cationic surfactant and in the presence of an emulsifyingaid composed of a glycol-based compound. The ratio of the surface-activeemulsifier is about 1 to 20% by weight and preferably about 1 to 10% byweight, and the ratio of the emulsifying aid is about 10 to 100% byweight and preferably about 15 to 70% by weight, based on the totalamount of the monomers for the copolymerization.

As such a cationic surfactant, a polyethylene oxide adduct of aquaternary ammonium-based surfactant, for example, an alkylammoniumchloride or alkylpyridinium salt having 1 to 3 polyoxyethylene groups,is used. On this occasion, a cationic surfactant without thepolyethylene oxide, for example, a quaternary ammonium-based surfactant,can be simultaneously used. In such a case, the weight ratio ispreferably about 0.1 to 2 to the polyethylene oxide adduct type.

In addition, as the polyethylene oxide adduct type nonionic surfactant,for example, a reaction product of a polyethylene oxide with an alcoholsuch as an aliphatic alcohol or an aromatic alcohol, an alkyl ether,oleic acid, a C.sub.12 to C.sub.18 alkylamine, or sorbitan mono fattyacid is used in a ratio of about 80% by weight or less and preferablyabout 30 to 80% by weight in the total amount with the polyethyleneoxide adduct type cationic surfactant.

Here, instead of the cationic surfactant, those in which an aminecompound having a polyethylene oxide chain, for example, apolyoxyethylene octadecylamine (such as Amiet-320, a Kao product), apolyoxyethylene alkyldiamine (such as Esoduomin T/25, a Lion product)represented by the general formula:H(OCH₂CH₂)_(x)NRCH₂CH₂CH₂N[(CH₂CH₂O)_(y)H](CH₂CH₂O)_(z)H,or a polyoxyethylene dodecylamine (such as Nymeen L-207, a NOF product)is neutralized with an organic acid such as acetic acid can be used.

Examples of the glycol compound as the emulsifying aid used in acombination with the emulsifier include ethylene glycol, polyethylene(n=2 to 4 or more) glycol, propylene glycol, polypropylene (n=2 to 4 ormore) glycol, their terminal monomethyl ethers, hexylene glycol, andpropylene glycol adducts of glycerin. A polypropylene glycol-basedcompound having a molecular weight of about 300 to 3000 or hexyleneglycol is preferably used.

Prior to the copolymerization reaction, a polymerizable monomer mixturecontaining a perfluoroalkylalkyl(meth)acrylate and another polymerizablemonomer is subjected to emulsification treatment in the presence of asurface-active emulsifier and an emulsifying aid. The emulsificationtreatment is sufficiently carried out using a high-pressure homogenizeror the like.

The copolymerization reaction of the emulsified polymerizable monomermixture is performed in the presence of a radical polymerizationinitiator added to the reaction system. The radical polymerizationinitiator may be any of organic peroxides, azo compounds, andpersulfates. Preferably, a water-soluble azo compound, for example,2,2′-azobis(2-amidinopropane).dihydrochloride, is used in a ratio ofabout 0.1 to 10% by weight and preferably about 0.5 to 7% by weight tothe total weight of the polymerizable monomer mixture.

The copolymerization reaction is carried out in an aqueous solvent atabout 40 to 80° C. for about 1 to 10 hours to form an aqueous dispersion(aqueous emulsion) serving as a stock solution having a solid contentconcentration of about 15 to 35% by weight. As the aqueous solvent, inaddition to the use of water alone, preferably used an aqueous solventscontaining about 1 to 30% by weight of a water-soluble organic solvent,for example, a ketone such as acetone or methyl ethyl ketone, an alcoholsuch as methanol or ethanol, or a glycol such as ethylene glycol,propylene glycol, dipropylene glycol, a monomethyl ether thereof, or atripropylene glycol. In the reaction, a molecular weight modifier may beused, and, for example, an alkyl mercaptan such as n-octyl mercaptan,n-dodecyl mercaptan, or tertiary dodecyl mercaptan is preferably used.

The thus obtained aqueous dispersion as the stock solution is dilutedwith water, preferably with ion-exchanged water to give a solid contentconcentration of about 0.1 to 10% by weight, and then is effectivelyapplied, as a water- and oil-repellent, to, for example, fibers, afabric, a woven fabric, paper, a film, a carpet, or a fabric productmade of filaments, threads, or fibers. The application is performed bycoating, dipping, spraying, padding, roll coating, or a combinationthereof. For example, a bath containing a solid content in aconcentration of about 0.1 to 10% by weight is used as a pad bath. Amaterial to be treated is padded in this pad bath and is then subjectedto removal of excessive liquid with a squeezing roller, followed bydrying, thereby allowing the fluorine-containing copolymer to adhere tothe material to be treated in a ratio of about 0.01 to 10% by weight tothe amount of the material. Subsequently, drying, which varies dependingon the type of the material to be treated, is usually conducted at about80 to 120° C. for about from 1 minute to 2 hours, and then curing isperformed under low curing temperature conditions of at 150 to 180° C.for about 1 to 3 minutes, preferably at about 150 to 170° C. for about 1to 3 minutes, and particularly preferably at 150° C. for 3 minutes tocomplete the water- and oil-repellent treatment.

EXAMPLES

Next, the present invention will be described with reference toExamples. Note that percentage in parentheses means % by weight.

Example 1

2-(n-Perfluorohexyl)ethyl methacrylate 78.5 g (61.6%) Benzylmethacrylate 22.4 g (17.6%) 2-Hydroxyethyl methacrylate 5.6 g (4.4%)Polyethylene glycol (n = 4) 4.2 g (3.3%) monomethacrylate (PE-200, a NOFproduct) Lauryl mercaptan (chain transfer agent) 0.5 g Polyoxyethylenepolycyclic phenyl ether 7.0 g (surfactant) (Newcol-740, a NipponNyukazai product) Acetone (solvent) 76.7 g Ion-exchanged water 225.8 g

The above-mentioned components were put in a 1-L glass reaction vesseland were mixed, and further subjected to emulsification mixing using ahigh-pressure homogenizer. The resulting emulsion was substituted bynitrogen gas for 30 minutes. Then, the inner temperature of the reactionvessel was gradually increased to 40° C., and then

vinylidene chloride 11.2 g (8.8%) N-methylol acrylamide (dissolved in5.6 g (4.4%) 29.3 g of ion-exchanged water) 2,2′-azobis(2- 2.8 gamidinopropane)•dihydrochloride (dissolved in 30.4 g of ion-exchangedwater)were added thereto (the total amount including 285.5 g of totalion-exchanged water was 500.0 g). Furthermore, the inner temperature wasgradually increased to 70° C., followed by the reaction at thetemperature for 4 hours. After the completion of the reaction andcooling, an aqueous dispersion having a solid content concentration of25.2% by weight was obtained. The melting point (DSC method) of thecopolymer separated from the aqueous dispersion was 44° C.

The thus obtained aqueous dispersion was diluted with ion-exchangedwater to a solid content concentration of 0.5% by weight, and a cottonfabric, a cotton/polyester blended fabric, a polyester fabric, or anylon fabric was immersed therein for measuring water-repellency(according to JIS L1092) and oil-repellency (according toAATCC-TM118-1992). The wet pick-ups after squeezing were 100% for thecotton fabric and the cotton blended fabric, 40% for the polyesterfabric, and 60% for the nylon fabric. The drying conditions were 80° C.for 10 minutes, and the curing conditions were 150° C. for 3 minutes,for all the fabrics.

The evaluation criteria for water-repellency were defined in conformitywith the rules of the above-mentioned JIS.

Degree of water-repellency Condition 100 Showing no wet state andadhesion of water droplets on the surface 90 Showing little adhesion ofwater droplets on the surface 80 Partially showing separate wet state onthe surface 70 Showing wet state on a half area of the surface 50Showing wet state on the entire surface 0 Showing complete wet state onboth surfaces

The evaluation criteria for oil-repellency were defined in conformitywith the rules of the above-mentioned AATCC. A drop of a test solutionwas dropped onto an oil-repellent treated fabric, and conditions at 30seconds after the dropping were investigated. When the test solutiondropped was held on the fabric, a test using a test solution having alarger number was further conducted. The oil-repellency was evaluatedwith the test solution that was the limit for being held on the fabricand on the basis of the oil-repellency evaluation shown in the followingtable (when Nujol is not held at all (100%), it is defined 0).

Surface tension Oil-repellency No. Test solution (mN/m, 25° C.) 8n-heptane 20.0 7 n-octane 21.8 6 n-decane 23.5 5 n-dodecane 25.0 4n-tetradecane 26.7 3 n-hexadecane 27.3 2 Nujol/n-hexadecane 29.6 (volumeratio: 65%:35%) 1 Nujol 31.2

In addition, textile feeling was evaluated by touching and evaluated atthe following four grades:

⊙: very soft

◯: soft

Δ: the same as or slightly harder than the original fabric

x: harder than the original fabric

Example 2

In Example 1, a copolymerization reaction was performed using the sameamount of 2-(n-perfluorobutyl)ethyl methacrylate instead of the2-(n-perfluorohexyl)ethyl methacrylate. The resulting diluted aqueousdispersion was subjected to water-repellency and oil-repellency testsand was evaluated for textile feeling.

Example 3

In Example 1, a copolymerization reaction was performed using the sameamount of 2-(n-perfluorohexyl)ethyl acrylate instead of the2-(n-perfluorohexyl)ethyl methacrylate. The resulting diluted aqueousdispersion was subjected to water-repellency and oil-repellency testsand was evaluated for textile feeling.

Example 4

In Example 1, a copolymerization reaction was performed using the sameamount of 2-(n-perfluorobutyl)ethyl acrylate instead of the2-(n-perfluorohexyl)ethyl methacrylate. The resulting diluted aqueousdispersion was subjected to water-repellency and oil-repellency testsand was evaluated for textile feeling.

Example 5

In Example 1, a copolymerization reaction was performed using 35.0 g ofhexylene glycol as an emulsifying aid, not using acetone, and changingthe total amount of ion-exchanged water to 327.2 g. The resultingdiluted aqueous dispersion was subjected to water-repellency andoil-repellency tests and was evaluated for textile feeling.

Example 6

In Example 1, a copolymerization reaction was performed by changing thecomponent amounts of the following components in the copolymerizingmonomers charged for the copolymerization reaction as follows:

2-(n-perfluorohexyl)ethyl methacrylate 87.2 g (64.0%) benzylmethacrylate 22.4 g (16.4%) 2-hydroxyethyl methacrylate 5.6 g (4.1%)polyethylene glycol (n = 4) monomethacrylate 4.2 g (3.1%) vinylidenechloride 11.2 g (8.2%)  N-methylol acrylamide 5.6 g (4.1%)and the resulting diluted aqueous dispersion was subjected towater-repellency and oil-repellency tests and was evaluated for textilefeeling. In addition, 35.0 g of hexylene glycol was used as anemulsifying aid, acetone was not used, and the total amount ofion-exchanged water was changed to 318.5 g.

Example 7

In Example 1, a copolymerization reaction was performed by changing thecomponent amounts of the following components in the copolymerizingmonomers charged for the copolymerization reaction as follows (providedthat N-methylol methacrylamide was used instead of N-methylolacrylamide):

2-(n-perfluorohexyl)ethyl methacrylate 100.6 g (79.1%)  benzylmethacrylate 7.4 g (5.8%) 2-hydroxyethyl methacrylate 5.6 g (4.4%)polyethylene glycol (n = 4) monomethacrylate 4.2 g (3.3%) vinylidenechloride 3.8 g (3.0%) N-methylol methacrylamide 5.6 g (4.4%)and the resulting diluted aqueous dispersion was subjected towater-repellency and oil-repellency tests and was evaluated for textilefeeling. In addition, 35.0 g of hexylene glycol was used as anemulsifying aid, acetone was not used, and the total amount ofion-exchanged water was changed to 327.5 g.

Example 8

In Example 1, a copolymerization reaction was performed by changing thecomponent amounts of the following components in the copolymerizingmonomers charged for the copolymerization reaction as follows:

2-(n-perfluorohexyl)ethyl methacrylate 58.3 g (45.6%) benzylmethacrylate 29.2 g (22.8%) 2-hydroxyethyl methacrylate 5.6 g (4.4%)polyethylene glycol (n = 4) monomethacrylate 11.7 g (9.1%)  vinylidenechloride 17.5 g (13.7%) N-methylol acrylamide 5.6 g (4.4%)and the resulting diluted aqueous dispersion was subjected towater-repellency and oil-repellency tests and was evaluated for textilefeeling. In addition, 35.0 g of hexylene glycol was used as anemulsifying aid, acetone was not used, and the total amount ofion-exchanged water was changed to 326.8 g.

Example 9

In Example 5, a copolymerization reaction was performed by changing thekind and the amount of the component (A),perfluoroalkylalkyl(meth)acrylate, in the copolymerizing monomerscharged for the copolymerization reaction as follows:

(a) 2-(n-perfluorohexyl)ethyl acrylate 7.9 g (6.2%) (b)2-(n-perfluorohexyl)ethyl methacrylate 70.6 g (55.4%)and the resulting diluted aqueous dispersion was subjected towater-repellency and oil-repellency tests and was evaluated for textilefeeling.

Example 10

In Example 5, a copolymerization reaction was performed by changing thekind and the amount of the component (A),perfluoroalkylalkyl(meth)acrylate, in the copolymerizing monomerscharged for the copolymerization reaction as follows:

(a) 2-(n-perfluorohexyl)ethyl acrylate 15.7 g (12.3%) (b)2-(n-perfluorohexyl)ethyl methacrylate 62.8 g (49.3%)and the resulting diluted aqueous dispersion was subjected towater-repellency and oil-repellency tests and was evaluated for textilefeeling.

Example 11

In Example 5, a copolymerization reaction was performed by changing thekind and the amount of the component (A),perfluoroalkylalkyl(meth)acrylate, in the copolymerizing monomerscharged for the copolymerization reaction as follows:

(a) 2-(n-perfluorohexyl)ethyl acrylate 23.6 g (18.5%) (b)2-(n-perfluorohexyl)ethyl methacrylate 54.9 g (43.1%)and the resulting diluted aqueous dispersion was subjected towater-repellency and oil-repellency tests and was evaluated for textilefeeling.

Comparative Example 1

In Example 1, a copolymerization reaction was performed by using thesame amount (the same ratio) of 2-(perfluoroalkyl)ethyl methacrylate(perfluoroalkyl group being a group mixture of C₆:6%, C₈:52%, C₁₀:24%,C₁₂:7%, C₁₄:2%, and total: 91%, and having an average number of carbonatoms of 8.8) instead of the 2-(n-perfluorohexyl)ethyl methacrylate inthe materials charged for the copolymerization reaction, and theresulting diluted aqueous dispersion was subjected to water-repellencyand oil-repellency tests and was evaluated for textile feeling.

Table 1 shows the results of Examples 1 to 11 and Comparative Example 1.The melting point (DSC method) of each of the resulting copolymers isalso shown in the table. Regarding the water-repellency and theoil-repellency, the evaluation results thereof are shown in the form ofwater-repellency evaluation/oil-repellency evaluation.

TABLE 1 Water-repellency evaluation/ Melting Oil-repellency evaluationpoint Cotton Blended Polyester Nylon Textile Example (° C.). fabricfabric fabric fabric feeling Example 1 44 100/3 100/5 100/5 100/6 ◯Example 2 —  70/4  80/4  70/4 100/4 ◯ Example 3 44  70/6  80/6  70/6 70/6 ◯ Example 4 —  70/4  50/4  70/4  70/5 ◯ Example 5 45 100/3 100/5100/5 100/6 ◯ Example 6 45 100/4 100/5 100/5 100/6 ⊙ Example 7 46 100/5100/5 100/6 100/6 ⊙ Example 8 45 100/1 100/4 100/4 100/5 ◯ Example 9 44100/4 100/5 100/6 100/6 ⊙ Example 10 44 100/5 100/5 100/6 100/6 ⊙Example 11 43 100/5 100/5 100/6 100/6 ◯ Comp. Ex. 1 84 100/5 100/6 100/6100/6 Δ

Example 12

2-(n-Perfluorohexyl)ethyl acrylate 13.4 g (9.1%)2-(n-Perfluorohexyl)ethyl methacrylate 53.4 g (36.4%) Stearyl acrylate74.2 g (50.5%) Lauryl mercaptan 0.5 g Stearyltrimethyl ammonium chloride7.8 g (surfactant) Polyoxyethylene polycyclic phenyl ether 9.2 g(Newcol-740) Polypropylene glycol (Uniol D-400, a NOF 28.5 g product,molecular weight: 400) Ion-exchanged water 244.1 gThe above-mentioned components were put in a 1-L glass reaction vesseland were mixed and further subjected to emulsification mixing using ahigh-pressure homogenizer. The resulting emulsion was substituted bynitrogen gas for 30 minutes. Then, the inner temperature of the reactionvessel was gradually increased to 40° C., and then

N-methylol acrylamide (dissolved in 5.9 g (4.0%) 30 g of ion-exchangedwater) 2,2′-azobis(2-amidinopropane)•dihydrochloride 3.0 g (dissolved in30 g of ion-exchanged water)were added thereto (the total amount including 304.1 g of totalion-exchanged water was 500.0 g). Furthermore, the inner temperature wasgradually increased to 70° C., followed by the reaction at thetemperature for 4 hours. After the completion of the reaction andcooling, an aqueous dispersion having a solid content concentration of32.8% by weight was obtained. The resulting aqueous dispersion wassubjected to water-repellency and oil-repellency tests and was evaluatedfor textile feeling, as in Example 1.

Example 13

2-(n-Perfluorohexyl)ethyl acrylate 13.4 g (8.9%)2-(n-Perfluorohexyl)ethyl methacrylate 53.4 g (35.4%) Stearyl acrylate41.2 g (27.3%) Stearyl methacrylate 33.1 g (21.9%) Lauryl mercaptan 0.5g Stearyltrimethyl ammonium chloride 3.7 g Distearyldimethyl ammoniumchloride 8.7 g (surfactant) Polyoxyethylene polycyclic phenyl ether 7.5g (Newcol-740) Polypropylene glycol (Uniol D-400, molecular 38.4 gweight: 400) Ion-exchanged water 197.3 gThe above-mentioned components were put in a 1-L glass reaction vesseland were mixed and further subjected to emulsification mixing using ahigh-pressure homogenizer. The resulting emulsion was substituted bynitrogen gas for 30 minutes. Then, the inner temperature of the reactionvessel was gradually increased to 40° C., and then

acrylamide (dissolved in 30 g of 3.9 g (2.6%) ion-exchanged water)N-methylol acrylamide (dissolved in 5.9 g (3.9%) 30 g of ion-exchangedwater) 2,2′-azobis(2-amidinopropane)•dihydrochloride 3.0 g (dissolved in30 g of ion-exchanged water)were added thereto (the total amount including 287.3 g of totalion-exchanged water was 500.0 g). Furthermore, the inner temperature wasgradually increased to 70° C., followed by the reaction at thetemperature for 4 hours. After the completion of the reaction andcooling, an aqueous dispersion having a solid content concentration of34.9% by weight was obtained. The resulting aqueous dispersion wassubjected to water-repellency and oil-repellency tests and was evaluatedfor textile feeling, as in Example 1.

Example 14

In Example 12, a copolymerization reaction was conducted by using 24.5 g(16.7%) of benzyl methacrylate and 49.7 g (33.8%) of 2-ethylhexylmethacrylate instead of the stearyl acrylate, and changing the amount ofthe stearyltrimethyl ammonium chloride to 3.7 g, the amount of thepolyoxyethylene polycyclic phenyl ether to 7.5 g, the amount of thepolypropylene glycol to 38.4 g, and the total amount of ion-exchangedwater to 300 g, respectively. The resulting aqueous dispersion wassubjected to water-repellency and oil-repellency tests and was evaluatedfor textile feeling.

Example 15

2-(n-Perfluorohexyl)ethyl acrylate 13.4 g (9.1%)2-(n-Perfluorohexyl)ethyl methacrylate 53.4 g (36.4%) Stearyl acrylate41.1 g (28.0%) Stearyl methacrylate 8.6 g (5.9%) Benzyl methacrylate24.5 g (16.7%) Lauryl mercaptan 0.5 g Stearyltrimethyl ammonium chloride7.8 g Polyoxyethylene polycyclic phenyl ether 7.5 g (Newcol-740)Polypropylene glycol (Uniol D-400, molecular 19.2 g weight: 400)Hexylene glycol (solvent) 19.2 g Ion-exchanged water 205.9 gThe above-mentioned components were put in a 1-L glass reaction vesseland were mixed and further subjected to emulsification mixing using ahigh-pressure homogenizer. The resulting emulsion was substituted bynitrogen gas for 30 minutes. Then, the inner temperature of the reactionvessel was gradually increased to 40° C., and then

2-hydroxyethyl methacrylate (dissolved in 2.8 g (1.9%) 30 g ofion-exchanged water) N-methylol acrylamide (dissolved in 3.1 g (2.1%) 30g of ion-exchanged water) 2,2′-azobis(2-amidinopropane)•dihydrochloride3.0 g (dissolved in 30 g of ion-exchanged water)were added thereto (the total amount including 295.9 g of totalion-exchanged water was 500.0 g). Furthermore, the inner temperature wasgradually increased to 70° C., followed by the reaction at thetemperature for 4 hours. After the completion of the reaction andcooling, an aqueous dispersion having a solid content concentration of32.0% by weight was obtained. The resulting aqueous dispersion wassubjected to water-repellency and oil-repellency tests and was evaluatedfor textile feeling, as in Example 1.

Example 16

2-(n-Perfluorohexyl)ethyl acrylate 15.7 g (10.7%)2-(n-Perfluorohexyl)ethyl methacrylate 62.9 g (42.8%) Stearyl acrylate21.5 g (14.6%) Benzyl methacrylate 12.5 g (8.5%) 2-Ethylhexylmethacrylate 28.8 g (19.6%) Lauryl mercaptan 0.5 g Stearyltrimethylammonium chloride 3.7 g Polyoxyethylene polycyclic phenyl ether 7.5 g(Newcol-740) Hexylene glycol 38.4 g Ion-exchanged water 210.0 gThe above-mentioned components were put in a 1-L glass reaction vesseland were mixed and further subjected to emulsification mixing using ahigh-pressure homogenizer. The resulting emulsion was substituted bynitrogen gas for 30 minutes. Then, the inner temperature of the reactionvessel was gradually increased to 40° C., and then

2-hydroxyethyl methacrylate (dissolved in 2.8 g (1.9%) 30 g ofion-exchanged water) N-methylol acrylamide (dissolved in 2.8 g (1.9%) 30g of ion-exchanged water) 2,2′-azobis(2-amidinopropane)•dihydrochloride3.0 g (dissolved in 30 g of ion-exchanged water)were added thereto (the total amount including 300.0 g of totalion-exchanged water was 500.0 g). Furthermore, the inner temperature wasgradually increased to 70° C., followed by the reaction at thetemperature for 4 hours. After the completion of the reaction andcooling, an aqueous dispersion having a solid content concentration of30.0% by weight was obtained. The resulting aqueous dispersion wassubjected to water-repellency and oil-repellency tests and was evaluatedfor textile feeling, as in Example 1.

Comparative Example 2

In Example 12, an aqueous dispersion obtained by not using2-(n-perfluorohexyl)ethyl acrylate and changing the amount of2-(n-perfluorohexyl)ethyl methacrylate to 66.8 g (45.5%) was subjectedto water-repellency and oil-repellency tests and was evaluated fortextile feeling, as in Example 1.

Comparative Example 3

In Example 12, an aqueous dispersion obtained by not using2-(n-perfluorohexyl)ethyl methacrylate and changing the amount of2-(n-perfluorohexyl)ethyl acrylate to 66.8 g (45.5%) was subjected towater-repellency and oil-repellency tests and was evaluated for textilefeeling, as in Example 1.

Table 2 shows the results of Examples 12 to 16 and Comparative Examples2 and 3. Regarding the water-repellency and the oil-repellency, theevaluation results thereof are shown in the form of water repellencyevaluation/oil repellency evaluation.

TABLE 2 Water-repellency evaluation/ Oil-repellency evaluation CottonBlended Polyester Nylon Textile Example fabric fabric fabric fabricfeeling Example 12 100/4 100/5 100/6 100/6 ⊙ Example 13 100/4 100/5100/6 100/6 ⊙ Example 14 100/4 100/5 100/6 100/6 ◯ Example 15 100/4100/5 100/6 100/6 ⊙ Example 16 100/5 100/5 100/6 100/6 ◯ Comp. Ex. 2100/2 100/3 100/4 100/4 ⊙ Comp. Ex. 3  70/5  70/6  80/6  80/7 ⊙

The invention claimed is:
 1. A water- and oil-repellent including, as anactive ingredient, a fluorine-containing copolymer comprising as acopolymerization unit: (a) 5 to 40 wt. % of a perfluoroalkylalkylacrylate represented by the general formula:C_(n)F_(2n+1)C_(m)H_(2m)OCOCH═CH₂  wherein n represents an integerconsisting of 4, 5, or 6; and m represents 1, 2, 3, or 4, (b) 35 to 60wt. % of a perfluoroalkylalkyl methacrylate represented by the generalformula:C_(n)F_(2n+1)C_(m)H_(2m)OCOC(CH₃)═CH₂  wherein n represents 4, 5, or 6;and m represents 1, 2, 3, or 4, (c) 5 to 40 wt. % of a fluorine-freepolymerizable monomer, and (d) 0.5 to 40 wt. % of a cross-linkablegroup-containing polymerizable monomer, wherein the only fluorinepolymerizable monomers in said fluorine-containing copolymer consist of(a) and (b).
 2. The water- and oil-repellent according to claim 1,wherein the component (c), fluorine-free polymerizable monomer, of thefluorine-containing copolymer is at least one of vinylidene chloride,stearyl acrylate, stearyl methacrylate, benzyl acrylate, and benzylmethacrylate.
 3. The water- and oil-repellent according to claim 1,wherein the component (d), cross-linkable group-containing polymerizablemonomer, of the fluorine-containing copolymer is a hydrophilic monomer.4. The water- and oil-repellent according to claim 1, enabling curingunder curing conditions of at 150° C. for 3 minutes.